CN103476722A - Optical glass, preform and optical element - Google Patents
Optical glass, preform and optical element Download PDFInfo
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- CN103476722A CN103476722A CN2012800159905A CN201280015990A CN103476722A CN 103476722 A CN103476722 A CN 103476722A CN 2012800159905 A CN2012800159905 A CN 2012800159905A CN 201280015990 A CN201280015990 A CN 201280015990A CN 103476722 A CN103476722 A CN 103476722A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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Abstract
Provided is an optical glass exhibiting enhanced transparency with regard to visible light and having a small Abbe number ([nu]d) and partial dispersion ratio ([theta]g,F) while the refraction index (nd) is within a desired range. The optical glass contains, relative to the entire amount of the glass in terms of oxides, 20.0% to 60.0% of an SiO2 component and more than 20.0% to 50.0% or less of a CaO component, a total of more than 0% and 20.0% or less of a BaO component and a K2O component, and has an Nb2O5 component content of 30.0% or less, wherein the partial dispersion ratio ([theta]g,F) and the Abbe number ([nu]d) satisfy the relationship of (-0.00162*[nu]d+0.63822) <= ([theta]g,F) <= (-0.00275*[nu]d+0.68125) when [nu]d <= 31 and satisfy the relationship of (-0.00162*[nu]d+0.63822) <= ([theta]g,F) <= (-0.00162*[nu]d+0.64622) when [nu]d > 31.
Description
Technical field
The present invention relates to opticglass, preform and optical element.
Background technology
Although it varies the optical system such as digital camera, pick up camera, all with the bleeding that is called as aberration.This aberration is classified into monochromatic aberration and chromatic aberation, and especially chromatic aberation depends on the material behavior of the lens that use in optical system strongly.
Usually, the convex lens of chromatic aberation by combining low dispersion and the concavees lens of high dispersion are proofreaied and correct, but only can proofread and correct the aberration of red area and green area by this combination, understand the aberration of residual blue region.The aberration of the blue region that this is not eliminated is called secondary spectrum.For proofreading and correct secondary spectrum, need to have been considered the optical design of trend of the g ray (435.835nm) of blue region.Now, as the index of the optical characteristics of having in mind in optical design, use partial dispersion than (θ g, F).In above-mentioned combination in the optical system of lens of the lens of low dispersion and high dispersion, by the lens place in low dispersion side, use partial dispersion than (θ g, F) large optical material, at the lens place of high dispersion side, use partial dispersion than (θ g, F) little optical material, can proofread and correct secondary spectrum well.
Partial dispersion is meaned by following formula (1) than (θ g, F).
θg，F=（n
g-n
F）/（n
F-n
C）……（1）
In opticglass, in the partial dispersion of the partial dispersion that means the short wavelength territory than (θ g, F) and Abbe number (ν
d) between, there is the relation of substantial linear.The straight line that means this relation be used in take partial dispersion than (θ g, F) as the longitudinal axis, with Abbe number (ν
d) for the straight line of 2 connections that will obtain the when Abbe number mapping of the partial dispersion of NSL7 and PBM2 on the rectangular coordinates of transverse axis means, be called as reference line (with reference to Fig. 1).Although according to the difference of each opticglass manufacturers and difference, each company is defined with almost equal slope and intercept as the normal glass of the benchmark of reference line.(NSL7 and PBM2 are the opticglass that Obara Corporation manufactures, the Abbe number (ν of PBM2
d) be 36.3, the Abbe number (ν that partial dispersion is 0.5828, NSL7 than (θ g, F)
d) be 60.5, partial dispersion is 0.5436 than (θ g, F).）
Herein, as the glass with high dispersion, the such opticglass shown in known for example patent documentation 1～3.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 03-005340 communique
Patent documentation 2: TOHKEMY 2006-219365 communique
Patent documentation 3: Japanese kokai publication sho 61-168551 communique
Summary of the invention
the problem that invention will solve
Yet in patent documentation 1～3, the partial dispersion of disclosed glass is than not little, insufficient while being used as the lens of proofreading and correct aforementioned secondary spectrum.In addition, in patent documentation 1～3, disclosed glassy phase is not high for the transparency of visible ray, insufficient while especially using in the purposes of visible light transmissive.That is, need Abbe number (ν
d) little and high dispersion, partial dispersion than (θ g, F) little and with respect to the transparency of visible ray high opticglass.
The present invention puts in view of the above problems and carries out, and its purpose is to obtain specific refractory power (n
d) in the expectation scope in and Abbe number (ν
d) little, partial dispersion than (θ g, F) little and opticglass and the preform that has used it and optical element that with respect to the transparency of visible ray, be improved.
for the scheme of dealing with problems
The inventor etc., in order to address the above problem, have carried out going deep into experimental study repeatedly, found that by being used in combination SiO
2composition and CaO composition are also established their content within the limits prescribed, can form stable glass, seek Abbe number (ν simultaneously
d) reduction, and can reduce the painted of glass.
In addition, find by using BaO composition and K
2in the O composition more than a kind, can obtain the high refractive index of expectation, and can obtain lower partial dispersion than (θ g, F).In addition, find to pass through Nb
2o
5the content of composition is established within the limits prescribed, can obtain low Abbe number and partial dispersion ratio, and can reduce the devitrification of glass, thereby completes the present invention.Meanwhile, find by being used in combination SiO
2composition and CaO composition are also established their content within the limits prescribed, are difficult for producing painted, devitrification when glass is reheated.
In addition, find to pass through Nb
2o
5the content of composition is established within the limits prescribed, can obtain high refractive index, low Abbe number, lower part dispersion ratio, and can reduce the devitrification of glass.
Particularly, the invention provides scheme as described below.
(1) a kind of opticglass, wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% and contain more than 20.0% and 60.0% following SiO
2composition and more than the CaO composition below 20.0 and 50.0%, Nb
2o
5the content of composition is below 30.0%, partial dispersion is than (θ g, F) scope in ν d≤31 and between Abbe number (ν d) meets (0.00162 * ν d+0.63822)≤(θ g, F) relation of≤(0.00275 * ν d+0.68125), meet the relation of (0.00162 * ν d+0.63822)≤(θ g, F)≤(0.00162 * ν d+0.64622) in the scope of ν d>31.
(2) according to (1) described opticglass, wherein, the total amount of glass that converts and form with respect to oxide compound, BaO composition and K
2the content sum of O composition is more than 0% and be below 20.0%.
(3), according to (1) or (2) described opticglass, wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the TiO that contains 0～20.0%
2composition.
(4), according to the described opticglass of any one in (1)～(3), wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the TiO that contains 0～10.0%
2composition.
(5) according to the described opticglass of any one in (1)～(4), wherein, the total amount of glass that converts and form with respect to oxide compound, Nb
2o
5composition and TiO
2the content sum of composition is more than 10.0% and below 40.0%.
(6), according to the described opticglass of any one in (1)～(5), wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the BaO composition that contains 0～25.0%.
(7), according to the described opticglass of any one in (1)～(6), wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the BaO composition that contains 0～20.0%.
(8) according to the described opticglass of any one in (1)～(7), wherein, the mol ratio (Nb that oxide compound converts and forms
2o
5+ BaO)/(TiO
2+ CaO) be more than 0.100.
(9) according to the described opticglass of any one in (1)～(8), wherein, the mol ratio TiO that oxide compound converts and forms
2/ Nb
2o
5be below 5.00.
(10) according to the described opticglass of any one in (1)～(9), wherein, the mol ratio TiO that oxide compound converts and forms
2/ Nb
2o
5be below 3.00.
(11) according to the described opticglass of any one in (1)～(10), wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% into:
Li
2o composition 0～25.0% and/or
Na
2o composition 0～25.0% and/or
K
2o composition 0～25.0% and/or
Cs
2o composition 0～10.0%.
(12) according to the described opticglass of any one in (1)～(11), wherein, the total amount of glass that converts and form with respect to oxide compound, Rn
2the O composition (in formula, Rn be in the group of selecting free Li, Na, K, Cs to form more than a kind) mole and be below 30.0%.
(13) according to the described opticglass of any one in (1)～(12), wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% into:
MgO composition 0～20.0% and/or
SrO composition 0～20.0% and/or
ZnO composition 0～30.0%.
(14) according to the described opticglass of any one in (1)～(13), wherein, the total amount of glass that converts and form with respect to oxide compound, the RO composition (in formula, R be in the group of selecting free Mg, Ca, Sr, Ba, Zn to form more than a kind) mole and be more than 20.0% and below 60.0%.
(15) according to the described opticglass of any one in (1)～(14), wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% into:
(16) according to the described opticglass of any one in (1)～(15), it has more than 1.70 and 2.20 following specific refractory poweres (nd), and has more than 20 and 40 following Abbe numbers (ν d).
(17) according to the described opticglass of any one in (1)～(16), its spectral-transmission favtor is shown as 70% wavelength (λ
70) be below 500nm.
(18) according to the described opticglass of any one in (1)～(17), wherein, the value that the transmissivity of the light (d ray) of the aforementioned wavelength 587.56nm that reheats the test film after test (A) obtains divided by the transmissivity of the aforementioned d ray that reheats the test film before test is more than 0.95.
(reheat test (A): test film 15mm * 15mm * 30mm is reheated, from the temperature that is warming up to high 80 ℃ of transition temperature (Tg) than each sample in 150 minutes for room temperature, at the temperature of high 80 ℃ of the second-order transition temperature than aforementioned opticglass (Tg), insulation is 30 minutes, then naturally cool to normal temperature, after the relative two sides by test film is ground to thickness 10mm, carry out visual observation.〕
(19) according to the described opticglass of any one in (1)～(18), wherein, the aforementioned transmissivity that reheats the front test film of test (A) becomes 70% wavelength X
70with the aforementioned λ that reheats the test film after test
70difference be below 20nm.
(reheat test (A): test film 15mm * 15mm * 30mm is reheated, from the temperature that is warming up to high 80 ℃ of transition temperature (Tg) than each sample in 150 minutes for room temperature, at the temperature of high 80 ℃ of the second-order transition temperature than aforementioned opticglass (Tg), insulation is 30 minutes, then naturally cool to normal temperature, after the relative two sides by test film is ground to thickness 10mm, carry out visual observation.〕
(20) a kind of attrition process with and/or the preform used of precision press molding, it is that the described opticglass of any one in (1)～(19) forms.
(21) a kind of optical element, it is the described opticglass of any one in (1)～(19) to be carried out to grinding and/or grinding forms.
(22) a kind of optical element, it is the described opticglass of any one in (1)～(19) to be carried out to precision press molding form.
the effect of invention
According to the present invention, by SiO
2be used in combination BaO composition and K in composition and CaO composition
2establishing within the limits prescribed more than a kind and by their content in the O composition, can seek high refractive index and the high dispersion of glass, and the partial dispersion of glass is than (θ g, F) and Abbe number (ν
d) between there is the relation of expectation, and can reduce the painted of glass.Therefore, can access specific refractory power (n
d) in the expectation scope in and Abbe number (ν
d) little, partial dispersion is less than (θ g, F), the high opticglass and used preform and the optical element of this opticglass with respect to the transparency of visible ray.
The accompanying drawing explanation
Fig. 1 is the longitudinal axis and Abbe number (ν for partial dispersion is shown than (θ g, F)
d) be the figure of the reference line shown in the rectangular coordinates of transverse axis.
Fig. 2 illustrates partial dispersion about the embodiment of the application's the 1st opticglass than (θ g, F) and Abbe number (ν
d) the figure of relation.
Fig. 3 illustrates partial dispersion about the embodiment of the application's the 2nd opticglass than (θ g, F) and Abbe number (ν
d) the figure of relation.
Embodiment
The total amount of glass that opticglass of the present invention converts and forms with respect to oxide compound, be calculated by mol% and contain more than 20.0% and 60.0% following SiO
2composition and more than the CaO composition below 20.0 and 50.0%, Nb
2o
5the content of composition is below 30.0%, partial dispersion is than (θ g, F) scope in ν d≤31 and between Abbe number (ν d) meets (0.00162 * ν d+0.63822)≤(θ g, F) relation of≤(0.00275 * ν d+0.68125), meet the relation of (0.00162 * ν d+0.63822)≤(θ g, F)≤(0.00162 * ν d+0.64622) in the scope of ν d>31.By being used in combination SiO
2composition and CaO composition are also established their content within the limits prescribed, can form stable glass, and can seek Abbe number (ν
d) reduction, and can reduce the painted of glass.In addition, by by Nb
2o
5the content of composition is established within the limits prescribed, can obtain low Abbe number, lower part dispersion ratio, and can reduce the devitrification of glass.Therefore, can access specific refractory power (n
d) in the expectation scope in and Abbe number (ν
d) little, partial dispersion is less than (θ g, F), the high opticglass and used its preform and optical element with respect to the transparency of visible ray.
Wherein, the total amount of glass that the 1st opticglass converts and forms with respect to oxide compound, be calculated by mol% by summation meter and contain more than BaO composition and K below 0% and 20.0%
2the O composition.By using BaO composition and K
2in the O composition more than a kind, can obtain the high refractive index of expectation, and can obtain more lower part dispersion than (θ g, F).Meanwhile, by being used in combination SiO
2composition and CaO composition are also established their content within the limits prescribed, are difficult for producing painted, devitrification when glass is reheated.Therefore, can access specific refractory power (n
d) in the expectation scope in and Abbe number (ν
d) little, partial dispersion is less and high and have the opticglass of high compression moulding and used preform and the optical element of this opticglass with respect to the transparency of visible ray than (θ g, F).
In addition, in the 2nd opticglass, by by SiO
2composition, CaO composition, Nb
2o
5the content of composition is established within the limits prescribed, can obtain high refractive index, and can obtain low Abbe number, partial dispersion ratio, and can reduce the devitrification of glass.Therefore, can access specific refractory power (n
d) in the expectation high scope in and Abbe number (ν
d) little, partial dispersion is less than (θ g, F), the high opticglass and used preform and the optical element of this opticglass with respect to the transparency of visible ray.
Below, the embodiment of opticglass of the present invention is elaborated, the present invention is not subject to any restriction of following embodiment, in the scope of purpose of the present invention, can suitably be changed to implement.In addition, for the place of carrying out repeat specification, the situation that suitably description thereof is omitted is arranged, but and the purport of non-limiting invention.
[glass ingredient]
Below narration forms the compositing range of each composition of opticglass of the present invention.In this manual, the content of each composition, as long as no dated especially, is all % by mole content meaned of using the total amount of glass formed with respect to the oxide compound conversion.Herein, " oxide compound convert form " refers to the oxide compound that uses as the raw material of glass constituent of the present invention in hypothesis, composite salt, metal fluoride etc. and becomes oxide compound in the situation that all decompose during melting, when total amount of this generation oxide compound is made as to 100 % by mole, the composition of each contained composition in statement glass.
<about essential component, arbitrarily composition>
SiO
2composition is for promoting stable glass to form, reduce as the opticglass composition of preferred devitrification (generation of crystallisate) not.Especially pass through SiO
2the content of composition is made as more than 20.0%, and the partial dispersion that can improve not significantly glass obtains the glass of devitrification resistance excellence with comparing.In addition, can reduce thus devitrification while reheating, painted.On the other hand, by by SiO
2the content of composition is made as below 60.0%, is difficult for reducing because the specific refractory power of glass becomes, thereby can be easy to obtain the high refractive index of expectation, and can suppress the rising of the partial dispersion ratio of glass.In addition, by by SiO
2the content of composition is made as below 60.0%, can keep well the meltbility of glass.Therefore, SiO
2the content of composition preferably establishes 20.0%, more preferably establish 21.0%, further preferably establish 24.0%, further preferably establish 27.0%, most preferably establish 30.0% for lower limit.In addition, this SiO
2the content of composition is preferably established 60.0%, more preferably establishes 50.0%, is most preferably established 45.0% for the upper limit.SiO
2composition can be used SiO as raw material
2, K
2siF
6, Na
2siF
6deng.
The CaO composition is for for obtaining the neccessary composition of the low and glass that devitrification resistance is high of Abbe number.Especially be made as more than 20.0% by the content by the CaO composition, can access the opticglass that Abbe number is low and devitrification resistance is high, and can improve the meltability of glass.On the other hand, by the content by the CaO composition, be made as below 50.0%, can in the rising of the reduction of the specific refractory power that suppresses glass, partial dispersion ratio, suppress the devitrification resistance variation of the glass that caused by the excessive CaO of containing composition.In addition, can reduce thus devitrification while reheating, painted.Therefore, the content of CaO composition, preferably more than 20.0%, is more preferably established and is limited to 24.0%, further, preferably more than 30.0%, further preferably establishes and is limited to 32.0%, most preferably sets and is limited to 33.5%.In addition, the content of this CaO composition is preferably established 50.0%, more preferably establishes 45.0%, further preferably establishes 43.0%, is most preferably established 40.0% for the upper limit.The CaO composition can be used CaCO as raw material
3, CaF
2deng.
Especially, in the 1st opticglass, preferably by summation meter, contain more than BaO composition and K below 0% and 20.0%
2the O composition.By containing this total content more than 0%, can access the glass of the lower part dispersion ratio with expectation.On the other hand, by this total content is made as below 20.0%, can suppress to contain by excessive devitrification resistance, the chemical durability variation that these compositions cause.Mole and (BaO+K therefore,
2o) preferably more than 0%, more preferably establish 0.5%, further preferably establish 1.0% for lower limit.In addition, this mole and (BaO+K
2o) preferably establish 20.0%, more preferably establish 15.0%, most preferably establish 10.0% for the upper limit.
Nb
2o
5composition is the composition of the devitrification resistance of raising glass, and is to reduce the composition of Abbe number and partial dispersion ratio in the specific refractory power that improves glass, and is any composition in opticglass of the present invention.Especially pass through Nb
2o
5the content of composition is made as below 30.0%, the rising of the melting temperature (Tm) in the time of can suppressing glass manufacture, and can reduce by the excessive Nb of containing
2o
5the devitrification that composition causes.Therefore, Nb
2o
5the content of composition is preferably established 30.0%, more preferably establishes 20.0%, is most preferably established 15.0% for the upper limit.In addition, although can not contain Nb
2o
5composition, but by containing the Nb more than 0%
2o
5the content of composition, can improve the specific refractory power of glass and further reduce Abbe number, and, can reduce the partial dispersion ratio of glass.In addition, by containing the Nb more than 0%
2o
5the content of composition, can improve the devitrification resistance of glass, the compression moulding that improves glass.Therefore, Nb
2o
5the content of composition is preferably more than 0%, more preferably establishes 3.0%, further preferably establishes 4.0%, further preferably establishes 5.0%, most preferably establishes 6.0% for lower limit.Nb
2o
5composition can be used Nb as raw material
2o
5deng.
TiO
2composition is to reduce the composition of Abbe number in the specific refractory power that improves glass, and is any composition in opticglass of the present invention.
Especially pass through TiO
2the content of composition is made as below 20.0%, more preferably is made as below 10.0%, can reduce painted, the internal transmission rate that improves glass of glass.In addition, by by TiO
2the content of composition is made as below 10.0%, because partial dispersion rises thereby can be easy to obtain the lower part dispersion ratio that approaches reference line than being difficult for.Therefore, TiO
2the content of composition is preferably established 20.0%, is more preferably established 15.0% for the upper limit, further preferably is less than 12.0%, further preferably establishes 10.0%, further preferably establishes 9.5%, most preferably establishes 9.0% for the upper limit.
On the other hand, from the viewpoint that obtains lower part dispersion ratio more, reduce painted viewpoint, preferably containing TiO
2composition, but from obtaining high refractive index more, lower Abbe number or from improving the viewpoint of devitrification resistance, this TiO
2the content of composition is preferably more than 0%, more preferably establishes 1.0%, further preferably establishes 3.0%, most preferably establishes 4.5% for lower limit.
TiO
2composition can be used TiO as raw material
2deng.
Especially in the 2nd opticglass, Nb
2o
5composition and TiO
2the content sum of composition is preferably more than 10.0% and below 40.0%.Especially due to it be more than 10.0%, improve the Nb that specific refractory power reduces Abbe number
2o
5composition and TiO
2the content of composition increases, and therefore can access high refractive index with expectation and the opticglass of low Abbe number.On the other hand, due to it be below 40.0%, the devitrification caused by these compositions can be reduced, therefore the glass that devitrification resistance is higher and stable can be accessed.Mole and (Nb therefore,
2o
5+ TiO
2) preferably establish 10.0%, more preferably establish 12.0%, further preferably establish 14.0%, most preferably establish 15.0% for lower limit.On the other hand, mole and (Nb
2o
5+ TiO
2) preferably establish 40.0%, more preferably establish 30.0%, further preferably establish 25.0%, most preferably establish 20.0% for the upper limit.
The BaO composition is the composition of the devitrification resistance of the specific refractory power that improves glass, the partial dispersion ratio that reduces glass and raising glass.Especially be made as below 25.0%, more preferably be made as below 20.0% by the content by the BaO composition, can suppress the devitrification resistance, the chemical durability variation that are caused by the excessive BaO of containing composition.Therefore, the content of BaO composition is preferably established 25.0%, more preferably establishes 20.0%, further preferably establishes 15.0%, is most preferably established 10.0% for the upper limit.In addition, because the BaO composition is any composition, can therefore not contain yet, but, by containing the BaO composition more than 0%, can improve meltability, devitrification resistance, and be easy to realize high refractive index and the lower part dispersion ratio of expectation.In addition, can reduce thus devitrification while reheating, painted.Therefore, the content of BaO composition can, preferably more than 0%, can more preferably be established 0.5%, further preferably establish 1.0% for lower limit.On the other hand, the BaO composition can be used BaCO as raw material
3, Ba (NO
3)
2deng.
In opticglass of the present invention, with respect to TiO
2the Nb of the content sum of composition and CaO composition
2o
5the content sum of composition and BaO composition is preferably more than 0.100.Thus, owing to improving the TiO of the composition of partial dispersion ratio with respect to conduct
2the content of composition and CaO composition, as the Nb of the composition that reduces the partial dispersion ratio
2o
5the content of composition and BaO composition increases, and therefore can access the opticglass of the lower part dispersion ratio with expectation.Therefore, the mol ratio (Nb that oxide compound converts and forms
2o
5+ BaO)/(TiO
2+ CaO) preferably establish 0.100, more preferably establish 0.120, further preferably establish 0.130, most preferably establish 0.140 for lower limit.On the other hand, to this mol ratio (Nb
2o
5+ BaO)/(TiO
2+ CaO) the upper limit is not particularly limited, this mol ratio (Nb of opticglass of the present invention
2o
5+ BaO)/(TiO
2+ CaO) be below 1.000, be more specifically below 0.700, further specifically the situation below 0.400 is more.
The mol ratio TiO that the oxide compound of opticglass of the present invention converts and forms
2/ Nb
2o
5be preferably below 5.00.Thus, the Abbe number of glass be adjusted in the scope of expectation and partial dispersion than reducing, therefore can access the opticglass of Abbe number with expectation and the relation of partial dispersion ratio.Meanwhile, can access painted few opticglass.Therefore, the mol ratio TiO that oxide compound converts and forms
2/ Nb
2o
5preferably establish 5.00, more preferably establish 4.00, further preferably establish 3.00, further preferably establish 2.50, further preferably establish 2.00 for the upper limit.Especially containing BaO composition and K
2in the 1st opticglass of at least one in the O composition as essential component, from the viewpoint of further reduction partial dispersion ratio, most preferably by this TiO
2/ Nb
2o
5be made as below 2.00.
Li
2the O composition is the meltbility that improves glass and the composition that reduces the partial dispersion ratio of glass, and is any composition in opticglass of the present invention.Especially pass through Li
2the content of O composition is made as below 25.0%, can, in the reduction that suppresses specific refractory power, reduce by the excessive Li that contains
2when glass that the O composition causes forms, the opacification in while reheating, crystallization, improve the chemical durability of glass simultaneously.Therefore, Li
2the content of O composition preferably establishes 25.0%, more preferably establish 17.0%, further preferably establish 12.0%, further preferably establish 9.5%, most preferably establish 5.0% for the upper limit.Li
2the O composition can be used Li as raw material
2cO
3, LiNO
3, LiF etc.
Na
2the O composition is the composition of the meltbility of raising glass, simultaneously for reducing the composition of glass transition point, and is any composition in opticglass of the present invention.Especially pass through Na
2the content of O composition is made as below 25.0%, can make the difficult reduction of specific refractory power, while chemical durability be difficult for variation.The devitrification when devitrification resistance in the time of in addition, can improving glass formation, reduction reheat, painted.Therefore, Na
2the content of O composition preferably establishes 25.0%, more preferably establish 15.0%, further preferably establish 10.0%, most preferably establish 5.0% for the upper limit.Na
2the O composition can be used Na as raw material
2cO
3, NaNO
3, NaF, Na
2siF
6deng.
K
2the O composition is to reduce the composition of glass transition point in the meltbility of adjusting glass, and is any composition in opticglass of the present invention.Especially pass through K
2the content of O composition is made as below 25.0%, the devitrification resistance in the time of can improving glass formation, devitrification when reduction reheats, painted.Therefore, K
2the content of O composition preferably establishes 25.0%, more preferably establish 20.0%, further preferably establish 15.0%, most preferably establish 10.0% for the upper limit.In addition, although can not contain K from the viewpoint that obtains the higher glass of compression moulding
2the O composition, but, owing to there being the effect that further reduces the partial dispersion ratio, therefore can preferably contain and be greater than 0%, the lower limit that can contain more preferably is made as 0.5%, further preferably is made as 1.0%.K
2the O composition can be used K as raw material
2cO
3, KNO
3, KF, KHF
2, K
2siF
6deng.
Cs
2the O composition is the composition of reduction glass transition point, and is any composition in opticglass of the present invention.Especially pass through Cs
2the content of O composition is made as below 10.0%, can reduce by the excessive Cs of containing
2the devitrification of the glass that the O composition causes.Therefore, Cs
2the content of O composition is preferably established 10.0%, more preferably establishes 5.0%, is further preferably established 3.0% for the upper limit.Cs
2the O composition can be used Cs as raw material
2cO
3, CsNO
3deng.
In opticglass of the present invention, Rn
2the O composition (in formula, Rn be in the group of selecting free Li, Na, K and Cs to form more than a kind) the content sum be preferably below 30.0%.Especially by should mole and be made as below 30.0%, can be easy to obtain expectation high refractive index, reduce the devitrification of glass simultaneously.Therefore, Rn
2the content of O composition mole and preferably establish 30.0%, more preferably establish 20.0%, further preferably establish 10.0%, further preferably establish 7.0%, most preferably establish 5.0% for the upper limit.
The MgO composition is the composition of the melt temperature of reduction glass, and is any composition in opticglass of the present invention.Especially be made as below 20.0% by the content by the MgO composition, can in the reduction of the specific refractory power that suppresses glass, improve the devitrification resistance of glass.In addition, can reduce thus devitrification while reheating, painted.Therefore, the content of MgO composition is preferably established 20.0%, more preferably establishes 10.0%, is most preferably established 5.0% for the upper limit.The MgO composition can be used MgO, MgCO as raw material
3, MgF
2deng.
The SrO composition for the specific refractory power that improves glass, improve glass devitrification resistance composition and be any composition in opticglass of the present invention.Especially be made as below 20.0% by the content by the SrO composition, can suppress the chemical durability variation of glass.Therefore, the content of SrO composition is preferably established 20.0%, more preferably establishes 15.0%, is most preferably established 10.0% for the upper limit.The SrO composition can be used Sr (NO as raw material
3)
2, SrF
2deng.
The ZnO composition is the devitrification resistance that improves glass, the composition that reduces glass transition point, and is any composition in opticglass of the present invention.Especially be made as below 30.0% by the content by the ZnO composition, improve the chemical durability of glass in can the devitrification when reducing the reheating of glass.In addition, can reduce thus devitrification while reheating, painted.Therefore, the content of ZnO composition is preferably established 30.0%, more preferably establishes 20.0%, further preferably establishes 16.0%, is most preferably established 10.0% for the upper limit.In addition, because the ZnO composition can not contain for any composition, but, from obtaining the viewpoint of extra high devitrification resistance and low glass transition point, the content of this ZnO composition can be preferably greater than 0%, can more preferably establish 0.5%, further preferably establish 1.0% for lower limit.The ZnO composition can be used ZnO, ZnF as raw material
2deng.
In opticglass of the present invention, the RO composition (in formula, R be in the group of selecting free Zn, Mg, Ca, Sr, Ba to form more than a kind) useful composition when in the devitrification resistance for improving glass, adjusting specific refractory power.Especially be made as more than 20.0% by the content by the RO composition, can improve the devitrification resistance of glass.On the other hand, when the total content of these RO compositions is too much, the devitrification resistance of glass is easy to variation on the contrary, and the chemical durability of glass also is easy to variation.Therefore, the total content of RO composition is preferably established 20.0%, more preferably establishes 25.0%, is further preferably established 30.0% for lower limit, most preferably more than 35.0%.In addition, the total content of this RO composition is preferably established 60.0%, more preferably establishes 55.0%, is most preferably established 50.0% for the upper limit.
P
2o
5composition is the composition of the stability of raising glass, and is any composition in opticglass of the present invention.Especially pass through P
2o
5the content of composition is made as below 30.0%, can reduce by the excessive P of containing
2o
5therefore the devitrification that composition causes, can improve the stability of glass.Therefore, P
2o
5the content of composition is preferably established 30.0%, more preferably establishes 20.0%, is most preferably established 10.0% for the upper limit.P
2o
5composition can be used Al (PO as raw material
3)
3, Ca (PO
3)
2, Ba (PO
3)
2, BPO
4, H
3pO
4deng.
B
2o
3composition forms, improves devitrification resistance for the stable glass of promotion and improves the composition of the meltability of glass, and is any composition in opticglass of the present invention.Especially pass through B
2o
3the content of composition is made as below 40.0%, can obtain the high refractive index of expectation by the reduction that suppresses specific refractory power, and can suppress the rising of the partial dispersion ratio of glass.In addition, the devitrification in the time of can reducing thus the reheating of glass.Therefore, B
2o
3the content of composition preferably establishes 40.0%, more preferably establish 30.0%, further preferably establish 20.0%, further preferably establish 15.0%, most preferably establish 10.0% for the upper limit.In addition, due to B
2o
3composition can not contain for any composition, but by containing the B more than 0%
2o
3composition, can improve devitrification resistance and the meltability of glass.Therefore, this B
2o
3the content of composition, preferably more than 0%, is more preferably established 1.0%, is most preferably established 2.0% for lower limit.B
2o
3composition can be used H as raw material
3bO
3, Na
2b
4o
7, Na
2b
4o
710H
2o, BPO
4deng.
GeO
2composition for the specific refractory power that improves glass, make the glass composition of the devitrification while stablizing to reduce moulding that becomes, and be any composition in opticglass of the present invention.Especially pass through GeO
2the content of composition is made as below 20.0%, can reduce expensive GeO
2therefore the consumption of composition, can reduce the material cost of glass.Therefore, GeO
2the content of composition preferably establishes 20.0%, more preferably establish 10.0%, further preferably establish 5.0%, most preferably establish 3.0% for the upper limit.GeO
2composition can be used GeO as raw material
2deng.
Y
2o
3composition, La
2o
3composition, Gd
2o
3composition and Yb
2o
3composition is to reduce the composition of partial dispersion ratio in the specific refractory power that improves glass, and is any composition in opticglass of the present invention.Especially pass through Y
2o
3composition, La
2o
3composition, Gd
2o
3composition and Yb
2o
3the content of composition is made as respectively below 15.0%, can improve the devitrification resistance of glass, and can suppress the rising of the Abbe number of glass.Therefore, Y
2o
3composition, La
2o
3composition, Gd
2o
3composition and Yb
2o
3composition content separately preferably establishes 15.0%, more preferably establish 10.0%, further preferably establish 7.0%, most preferably establish 4.2% for the upper limit.Y
2o
3composition, La
2o
3composition, Gd
2o
3composition and Yb
2o
3composition can be used Y as raw material
2o
3, YF
3, La
2o
3, La (NO
3)
3xH
2o(X is integer arbitrarily), Gd
2o
3, GdF
3, Yb
2o
3deng.
Ta
2o
5composition is the composition of the devitrification resistance of the specific refractory power that improves glass, the Abbe number that reduces glass and partial dispersion ratio and raising glass, and is any composition in opticglass of the present invention.Especially pass through Ta
2o
5the content of composition is made as below 15.0%, at the Ta reduced as the rare mineral resource
2o
5in the time of the consumption of composition, glass becomes and is easy to melt under lower temperature, therefore can reduce the production cost of glass.In addition, by by Ta
2o
5the content of composition is made as below 15.0%, can reduce by the excessive Ta of containing
2o
5the devitrification of the glass that composition causes.Therefore, Ta
2o
5the content of composition is preferably established 15.0%, more preferably establishes 10.0%, is most preferably established 5.0% for the upper limit.Ta
2o
5composition can be used Ta as raw material
2o
5deng.
Bi
2o
3the specific refractory power that composition is raising glass also reduces Abbe number and the composition of reduction glass transition point, and be any composition in opticglass of the present invention.Especially pass through Bi
2o
3the content of composition is made as below 15.0%, can make the partial dispersion of glass rise than being difficult for.In addition, by by Bi
2o
3the content of composition is made as below 15.0%, can reduce the painted of glass, can improve the internal transmission rate of glass.Therefore, Bi
2o
3the content of composition is preferably established 15.0%, more preferably establishes 10.0%, is most preferably established 5.0% for the upper limit.Bi
2o
3composition can be used Bi as raw material
2o
3deng.
WO
3composition is for the specific refractory power that improves glass and reduce Abbe number, improve glass devitrification resistance, improve the composition of the meltability of glass, and be any composition in opticglass of the present invention.Especially pass through WO
3the content of composition is made as below 20.0%, can make the partial dispersion of glass increase than being difficult for.In addition, by by WO
3the content of composition is made as below 20.0%, can reduce painted, the internal transmission rate that improves glass of glass.Therefore, WO
3the content of composition is preferably established 20.0%, more preferably establishes 10.0%, is most preferably established 5.0% for the upper limit.WO
3composition can be used WO as raw material
3deng.
TeO
2composition is the composition of the specific refractory power that improves glass, the partial dispersion ratio that reduces glass, reduction glass transition point, and is any composition in opticglass of the present invention.Especially pass through TeO
2the content of composition is made as below 30.0%, can reduce glass painted, improve the transmissivity of glassy phase for visible ray.In addition, by reducing expensive TeO
2the use of composition, can access the glass that material cost is more cheap.Therefore, TeO
2the content of composition is preferably established 30.0%, more preferably establishes 20.0%, is most preferably established 10.0% for the upper limit.TeO
2composition can be used TeO as raw material
2deng.
ZrO
2composition improves the composition of devitrification resistance in for the specific refractory power improving glass and Abbe number, reduction partial dispersion ratio in the lump, and is any composition in opticglass of the present invention.Especially pass through ZrO
2the content of composition is made as below 15.0%, can reduce the devitrification of glass, and can be easy to obtain the more glass of homogeneous.Therefore, ZrO
2the content of composition is preferably established 15.0%, more preferably establishes 12.0%, is most preferably established 10.0% for the upper limit.In addition, although can not contain ZrO
2composition, but by containing the ZrO more than 0%
2composition can be easy to make the partial dispersion of glass than lower in the specific refractory power that improves glass and Abbe number.In addition, can reduce thus devitrification while reheating, painted.Therefore, ZrO
2the content of composition, preferably more than 0%, is more preferably established 1.0%, is further preferably established 2.0% for lower limit.ZrO
2composition can be used ZrO as raw material
2, ZrF
4deng.
Al
2o
3composition is the chemical durability that improves glass, the composition that improves the devitrification resistance of glass, and is any composition in opticglass of the present invention.Especially pass through Al
2o
3the content of composition is made as below 15.0%, can reduce by the excessive Al of containing
2o
3the devitrification that composition causes.In addition, can reduce thus devitrification while reheating, painted.Therefore, Al
2o
3the content of composition is preferably established 15.0%, more preferably establishes 10.0%, is most preferably established 5.0% for the upper limit.Al
2o
3composition can be used Al as raw material
2o
3, Al (OH)
3, AlF
3deng.
Sb
2o
3composition for the deaeration that promotes glass, make the composition of glass clarifying, and be any composition in opticglass of the present invention.Sb
2o
3composition, by being made as with respect to the content of the total amount of glass below 1.0%, is difficult in the time of can making glass melting excessively producing and bubbling, and can make Sb
2o
3composition is difficult for and melting equipment precious metals such as (especially) Pt alloying.Therefore, Sb
2o
3the content of composition is preferably established 1.0%, more preferably establishes 0.8%, is further preferably established 0.6% for the upper limit.But, in the situation that pay attention to the impact of opticglass on environment, preferably not containing Sb
2o
3composition.Sb
2o
3composition can be used Sb as raw material
2o
3, Sb
2o
5, Na
2h
2sb
2o
75H
2o etc.
In addition, the composition of glass clarifying, deaeration is not limited to above-mentioned Sb
2o
3composition, can be used known finings, deaerating agent or their combination in the field of glass manufacture.
<about the composition that should not contain>
Then, the composition that should not contain in opticglass of the present invention and the composition preferably do not contained are described.
Can in the scope of the characteristic that can't harm glass, add as required other compositions in opticglass of the present invention.
Wherein, except Ti, Zr, Nb, even each transiting metal components such as V, Cr, Mn, Co, Ni, Cu, Ag and Mo are in the situation that contain on a small quantity respectively independently or compound, also can make glass coloring, the certain wave strong point had in visibility region produces the character absorbed, therefore especially in the opticglass of the wavelength that uses visibility region, preferably be substantially free of.
In addition, lead compound and the As such as PbO
2o
3exist as harmful chemical substance in recent years and control the tendency of using Deng each composition of arsenic compound and Th, Cd, Tl, Os, Be, Se, not only in the manufacturing process of glass, even manufacturing procedure and form product after processing on all need the measure on environmental cure.Therefore, in the situation that pay attention to the impact on environment, except inevitably sneaking into, preferably be substantially free of these.Thus, be substantially free of the material of contaminate environment in opticglass.Therefore, even do not take the measure on the environmental cure of Te Do, also can manufacture, process and discard this opticglass.
As opticglass of the present invention and the glass preferably used, its composition is used % by mole meaning of the total amount of glass that convert to form with respect to oxide compound, therefore not directly with the record of quality %, mean, the composition meaned based on quality % that meets in the present invention each composition existed in the glass composition of desired each characteristic converts to form by oxide compound and roughly gets following value.
The composition meaned based on quality % of each composition especially, existed in the 1st opticglass converts to form by oxide compound and roughly gets following value.
The composition meaned based on quality % of each composition existed in the 2nd opticglass in addition, converts to form by oxide compound and roughly gets following value.
[manufacture method]
Opticglass of the present invention can for example be made as shown below.; mode above-mentioned raw materials is divided into by each one-tenth in the scope of content of regulation is mixed equably; the mixture of making is dropped into to platinum crucible, quartz crucible or alumina crucible thick melting; then put into golden crucible, platinum crucible, platinum alloy crucible or iridium crucible and carry out melting in 3～5 hours under the temperature range of 1100～1400 ℃; stirring homogenizes and carries out froth breaking etc.; then be down to the temperature of 1000～1300 ℃; then carry out final the stirring and remove striped; be poured into metal die Slow cooling, make thus.
<physical property>
Opticglass of the present invention preferably has specific refractory power and the dispersion (Abbe number) of regulation.More specifically, the specific refractory power (n of opticglass of the present invention
d) preferably establish 1.70, more preferably establish 1.75, most preferably establish 1.78 for lower limit.On the other hand, to the specific refractory power (n of opticglass of the present invention
d) the upper limit be not particularly limited, be roughly below 2.20, be more specifically below 2.10, be more specifically below 2.00, be that situation below 1.95 is more more specifically.In addition, the Abbe number (ν of opticglass of the present invention
d) preferably establish 40, more preferably establish 38, most preferably establish 35 for the upper limit.On the other hand, to the Abbe number (ν of opticglass of the present invention
d) lower limit be not particularly limited, be roughly more than 20, be more specifically more than 25, be that situation more than 27 is more more specifically.By these, it is wide that the degree of freedom of optical design becomes, even further seek the slimming of element, also can obtain large refraction of light amount.
In addition, opticglass of the present invention has the lower part dispersion than (θ g, F).More specifically, the partial dispersion of opticglass of the present invention is than (θ g, F) and Abbe number (ν
d) between meet (0.00162 * ν in the scope of ν d≤31
d+ 0.63822) relation of≤(θ g, F)≤(0.00275 * ν d+0.68125), and at ν
d>31 scope meets the relation of (0.00162 * ν d+0.63822)≤(θ g, F)≤(0.00162 * ν d+0.64622).Thus, can access have approach reference line partial dispersion than the opticglass of (θ g, F), therefore can reduce the chromatic aberation of the optical element formed by this opticglass.Herein, ν
dthe partial dispersion of the opticglass of≤31 o'clock is preferably (0.00162 * ν d+0.63822) than the lower limit of (θ g, F), and more preferably (0.00162 * ν d+0.63922), most preferably be (0.00162 * ν d+0.64022).On the other hand, the partial dispersion of the opticglass of ν d≤31 o'clock is than (θ g, F) the upper limit is preferably (0.00275 * ν d+0.68125), and more preferably (0.00275 * ν d+0.68025), most preferably be (0.00275 * ν d+0.67925).In addition, ν
dthe partial dispersion of the opticglass of>31 o'clock is preferably (0.00162 * ν d+0.63822) than the lower limit of (θ g, F), and more preferably (0.00162 * ν d+0.63922), most preferably be (0.00162 * ν d+0.64022).On the other hand, ν
dthe partial dispersion of the opticglass of>31 o'clock is preferably (0.00162 * ν d+0.64622) than the upper limit of (θ g, F), and more preferably (0.00162 * ν d+0.64522), most preferably be (0.00162 * ν d+0.64422).In addition, especially at Abbe number (ν
d) little zone, the partial dispersion of general glass is in the value higher than reference line than (θ g, F), and the partial dispersion of general glass is than (θ g, F) and Abbe number (ν
d) relation with curve representation.Yet, because this curve is difficult to be similar to, therefore in the present invention, use with ν
d=31 straight lines that have a Different Slope for boundary mean the situation lower than (θ g, F) than partial dispersion with general glassy phase.
In addition, opticglass of the present invention is preferably painted few.Especially, when opticglass of the present invention means with the transmissivity of glass, in the sample of thickness 10mm, spectral-transmission favtor shows 70% wavelength (λ
70) be below 500nm, more preferably, below 470nm, more preferably, below 450nm, most preferably be below 430nm.In addition, when opticglass of the present invention means with the transmissivity of glass, in the sample of thickness 10mm, spectral-transmission favtor shows 80% wavelength (λ
80) be below 560nm, more preferably, below 540nm, most preferably be below 520nm.In addition, opticglass of the present invention spectral-transmission favtor in the sample of thickness 10mm shows 5% wavelength (λ
5) be below 420nm, more preferably, below 400nm, most preferably be below 380nm.Thus, make the absorption limit of glass be positioned near ultraviolet region, the transparency of the glass under visibility region is improved, and therefore can preferably use the material of this opticglass as optical elements such as lens.
In addition, the compression moulding of opticglass of the present invention is preferably well.That is the value that, the transmissivity of the light (d ray) of the wavelength 587.56nm that reheats the test film after test (A) of opticglass of the present invention obtains divided by the transmissivity of the d ray that reheats the test film before test is preferably more than 0.95.In addition, the transmissivity that reheats the front test film of test (A) becomes 70% wavelength X
70with the λ that reheats the test film after test
70difference be preferably below 20nm.Thus, even the test that reheats of the hot repressing system that is assumed to processing also is difficult for producing devitrification and painted, therefore be difficult for losing the light transmittance of glass, therefore can easily to glass, carry out being processed as with hot repressing system the processing that reheats of representative.That is,, owing to making complex-shaped optical element by compression moulding, therefore can realize manufacturing cost cheaply and the manufacture of the optical element that productivity is good.
Reheating value that the transmissivity of light (d ray) of the wavelength 587.56nm of the test film after test (A) obtains divided by the transmissivity of the d ray that reheats the front test film of test (A) herein, preferably establishes 0.95, more preferably establishes 0.96, most preferably establishes 0.97 for lower limit.In addition, reheat the λ of the front test film of test (A)
70with the λ that reheats the test film after test (A)
70difference preferably to establish 20nm, more preferably establish 18nm, most preferably establish 16nm be the upper limit.
In addition, reheating test (A) carries out as follows: test film 15mm * 15mm * 30mm is reheated, from the temperature that is warming up to high 80 ℃ of transition temperature (Tg) than each sample in 150 minutes for room temperature, at the temperature of high 80 ℃ of the second-order transition temperature than aforementioned opticglass (Tg), insulation is 30 minutes, then naturally cool to normal temperature, after the relative two sides by test film is ground to thickness 10mm, carry out visual observation.
[preform and optical element]
Can be used by the opticglass of made the method for making the compression moldings such as type, precision press molding such as hot repressing to make glass forming body.; can make the preform that compression molding is used by opticglass; this preform is carried out to hot repressing and make type; then carry out attrition process and make glass forming body, or can be for example to carrying out preform that attrition process makes, carry out precision press molding and make glass forming body.In addition, the method for making glass forming body is not limited to these methods.
The glass forming body that operates like this and make is useful in various optical elements, especially preferably in the purposes of the optical elements such as lens, prism, uses therein.Thus, can reduce the bleeding of the color caused by chromatic aberation in the transmitted light of the optical system that is provided with optical element.Therefore, in the situation that this optical element is used for to photographic camera, can show more accurately the photography target thing, in the situation that this optical element is used for to projector, the reflection that more highly excellence ground projection is expected.
Embodiment
The composition of embodiments of the invention (No.1～No.57) and comparative example (No.A～No.D) and specific refractory power (n
d), Abbe number (ν
d), partial dispersion is shown as 5%, 70% and 80% wavelength (λ than (θ g, F), spectral-transmission favtor
5, λ
70, λ
80) and the change that reheats the transmissivity before and after test (A) be shown in table 1～table 9.Wherein, list the embodiment of embodiment 1～42 as the 1st opticglass.In addition, list embodiment 1,2,4～11,13,14,16～20,23,30 and 36～57 embodiment as the 2nd opticglass.In addition, following embodiment is only illustrative purpose, not only is defined in these embodiment.
In the glass of embodiments of the invention and comparative example, raw material as each composition, all select suitable separately oxide compound, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, the highly purified raw material used in the common opticglass such as metaphosphoric acid compound, in the mode weighing of the ratio of the composition that forms each embodiment shown in table 1～table 9 and comparative example and evenly mix, then drop into platinum crucible, the melting difficulty formed with glass is corresponding carries out melting in 3～5 hours the temperature range of 1100～1400 ℃ by electric furnace, stirring homogenizes and carries out froth breaking etc., then being cooled to 1000～1300 ℃ also stirs and homogenizes, be poured into again metal die, Slow cooling is made glass.
Herein, the specific refractory power (n of the glass of embodiment and comparative example
d), Abbe number (ν
d) and partial dispersion than (θ g, F), based on the industry of Japanese optics nitre, can measure by standard JOGIS01-2003.And, for tried to achieve Abbe number (ν
d) and partial dispersion than the value of (θ g, F), obtain relational expression (θ g, F)=-a * ν
dslope a in+b is 0.00162 and the intercept b of 0.00275 o'clock.In addition, the glass used in this mensuration is used the Slow cooling cooling rate is made as to-25 ℃/hr, by the Slow cooling stove, has carried out the glass of processing.
In addition, the transmissivity of the glass of embodiment and comparative example can be measured by standard JOGIS02 according to Japanese optics nitre industry.In addition, in the present invention, by measuring the transmissivity of glass, obtain painted the having or not and degree of glass.Particularly, the spectral-transmission favtor that the parallel grinding object in the opposite of thickness 10 ± 0.1mm is measured to 200～800nm according to JISZ8722, obtain λ
5(wavelength during transmissivity 5%), λ
70(wavelength during transmissivity 70%) and λ
80(wavelength during transmissivity 80%).
In addition, the change mensuration as described below of the transmissivity that reheats test (A) front and back of the glass of embodiment and comparative example.
Reheat value that the transmissivity of light (d ray) of the wavelength 587.56nm of the test film after test (A) obtains divided by the transmissivity of the d ray that reheats the test film before test and carry out according to the industrial meeting of Japanese optics nitre standard JOGIS02-2003 with respect to the glass reheated before and after test (A).Particularly, the parallel grinding object in the opposite of thickness 10 ± 0.1mm is measured to the spectral-transmission favtor of d ray according to JISZ8722, obtain (reheat test (A) after d radiant transmittance)/(reheating the front d radiant transmittance of test (A)), estimate the variation of the maximum transmission rate that reheats test (A) front and back.
On the other hand, the transmissivity that reheats the front test film of test (A) becomes 70% wavelength X
70with the λ that reheats the test film after test
70difference with respect to the glass reheated before and after test (A), obtain λ by above-mentioned test method
70(wavelength during transmissivity 70%), estimate the λ that reheats the front test film of test (A)
70with the λ that reheats the test film after test (A)
70poor.
Herein, reheating test (A) carries out as follows: the test film of 15mm * 15mm * 30mm is loaded on the matrix refractory body and puts into electric furnace reheat, from the temperature (falling into the temperature of refractory body) that is warming up to high 80 ℃ of transition temperature (Tg) than each sample in 150 minutes for normal temperature, at this temperature, insulation is 30 minutes, then be cooled to normal temperature and be taken out to outside stove, by observing inner mode, relative two sides is ground to thickness 10mm, then the glass specimen ground is carried out to visual observation.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
As shown in table 1～table 9, the opticglass of embodiments of the invention is at ν
dwithin≤31 o'clock, partial dispersion is (0.00275 * ν than (θ g, F)
d+ 0.68125), below, be more specifically below (0.00275 * ν d+0.67991).In addition, in ν d>31 o'clock partial dispersion, than (θ g, F), be below (0.00162 * ν d+0.64622), be more specifically below (0.00162 * ν d+0.64476).On the other hand, the partial dispersion of the opticglass of embodiments of the invention is more than (0.00162 * ν d+0.63822) than (θ g, F), is more specifically more than (0.00162 * ν d+0.64094).That is, about the partial dispersion of the glass of the application's embodiment than (θ g, F) and Abbe number (ν
d) relation as shown in Fig. 2 (the 1st opticglass) and Fig. 3 (the 2nd opticglass).Thus, known these partial dispersions than (θ g, F) in the expectation scope in.
On the other hand, the ν d of the glass of comparative example of the present invention (No.A～No.D)>31, and partial dispersion surpasses (0.00162 * ν d+0.64622) than (θ g, F).Therefore, clearly with the glassy phase ratio of comparative example, the opticglass of embodiments of the invention with Abbe number (ν
d) relational expression in partial dispersion less than (θ g, F).
In addition, the specific refractory power (n of the opticglass of embodiments of the invention
d) be more than 1.70, be more specifically more than 1.78, this specific refractory power (n simultaneously
d) be below 2.20, be more specifically below 1.85, in the scope for expectation.
In addition, the Abbe number (ν of the opticglass of embodiments of the invention
d) be more than 20, be more specifically more than 30, this Abbe number (ν simultaneously
d) be below 40, be more specifically below 34, in the scope for expectation.On the other hand, the ν of the glass of comparative example of the present invention (No.B)
dsurpassed 34.Therefore, the glassy phase of the opticglass of clear and definite embodiments of the invention and comparative example (No.B) is than Abbe number (ν
d) little.
In addition, the value that the transmissivity of the d ray that reheats the test film after test (A) of the opticglass of embodiments of the invention obtains divided by the transmissivity of the d ray that reheats the test film before test is more than 0.95, be more specifically more than 0.97, in the scope for expectation.In addition, the transmissivity λ of the test film that reheats test (A) front and back of the opticglass of embodiments of the invention
70difference be below 20nm, be more specifically below 15nm, for the expectation scope in.On the other hand, the value that the transmissivity of the d ray that reheats the test film after test (A) of the glass of comparative example of the present invention (No.A, No.B) obtains divided by the transmissivity of the d ray that reheats the test film before test is less than 0.95, after reheating test (A), with respect to the transmissivity of whole wavelength of visible ray, be less than 70%.Therefore, the glassy phase of the opticglass of clear and definite embodiments of the invention and comparative example (No.A, No.B) produces by reheating painted, the devitrification caused than being difficult for.
In addition, the λ of the opticglass of embodiments of the invention
70(wavelength during transmissivity 70%) is below 500nm, is more specifically below 407nm.In addition, the λ of the opticglass of embodiments of the invention
5(wavelength during transmissivity 5%) is below 420nm, is more specifically below 359nm.In addition, the λ of the opticglass of embodiments of the invention
80(wavelength during transmissivity 80%) is below 560nm, is more specifically below 463nm.Therefore, the opticglass of clear and definite embodiments of the invention, not easy coloring high with respect to the transmissivity of visible ray.
Therefore, the specific refractory power (n of the opticglass of clear and definite embodiments of the invention
d) and Abbe number (ν
d) high and chromatic aberation is little and have high compression moulding in scope in expectation and with respect to the transmissivity of visible ray.
Above, understand in detail the present invention to be exemplified as purpose, but the present embodiment is only only illustrative purpose, please understand and can not carry out many changes by those skilled in the art with not breaking away from thought of the present invention and scope.
Claims (22)
1. an opticglass, wherein, with respect to the total amount of glass of oxide compound conversion composition, be calculated by mol% and contain more than 20.0% and 60.0% following SiO
2composition and more than the CaO composition below 20.0 and 50.0%, Nb
2o
5the content of composition is below 30.0%, partial dispersion is than (θ g, F) scope in ν d≤31 and between Abbe number (ν d) meets (0.00162 * ν d+0.63822)≤(θ g, F) relation of≤(0.00275 * ν d+0.68125), meet the relation of (0.00162 * ν d+0.63822)≤(θ g, F)≤(0.00162 * ν d+0.64622) in the scope of ν d>31.
2. opticglass according to claim 1, wherein, the total amount of glass that converts and form with respect to oxide compound, BaO composition and K
2the content sum of O composition is more than 0% and be below 20.0%.
3. opticglass according to claim 1 and 2, wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the TiO that contains 0～20.0%
2composition.
4. according to the described opticglass of any one in claim 1～3, wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the TiO that contains 0～10.0%
2composition.
5. according to the described opticglass of any one in claim 1～4, wherein, the total amount of glass that converts and form with respect to oxide compound, Nb
2o
5composition and TiO
2the content sum of composition is more than 10.0% and below 40.0%.
6. according to the described opticglass of any one in claim 1～5, wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the BaO composition that contains 0～25.0%.
7. according to the described opticglass of any one in claim 1～6, wherein, the total amount of glass that converts and form with respect to oxide compound, be calculated by mol% the BaO composition that contains 0～20.0%.
8. according to the described opticglass of any one in claim 1～7, wherein, the mol ratio (Nb that oxide compound converts and forms
2o
5+ BaO)/(TiO
2+ CaO) be more than 0.100.
9. according to the described opticglass of any one in claim 1～8, wherein, the mol ratio TiO that oxide compound converts and forms
2/ Nb
2o
5be below 5.00.
10. according to the described opticglass of any one in claim 1～9, wherein, the mol ratio TiO that oxide compound converts and forms
2/ Nb
2o
5be below 3.00.
11. according to the described opticglass of any one in claim 1～10, wherein, the total amount of glass convert formed with respect to oxide compound, be calculated by mol% into:
Li
2o composition 0～25.0% and/or
Na
2o composition 0～25.0% and/or
K
2o composition 0～25.0% and/or
Cs
2o composition 0～10.0%.
12. according to the described opticglass of any one in claim 1～11, wherein, the total amount of glass that converts and form with respect to oxide compound, Rn
2the O composition mole and be below 30.0%, formula Rn
2in O, Rn be in the group of selecting free Li, Na, K, Cs to form more than a kind.
13. according to the described opticglass of any one in claim 1～12, wherein, the total amount of glass convert formed with respect to oxide compound, be calculated by mol% into:
MgO composition 0～20.0% and/or
SrO composition 0～20.0% and/or
ZnO composition 0～30.0%.
14. according to the described opticglass of any one in claim 1～13, wherein, the total amount of glass convert formed with respect to oxide compound, the RO composition mole and be more than 20.0% and below 60.0%, in formula RO, R be in the group of selecting free Mg, Ca, Sr, Ba, Zn to form more than a kind.
15. according to the described opticglass of any one in claim 1～14, wherein, the total amount of glass convert formed with respect to oxide compound, be calculated by mol% into:
16. according to the described opticglass of any one in claim 1～15, it has more than 1.70 and 2.20 following specific refractory poweres (nd), and has more than 20 and 40 following Abbe numbers (ν d).
17., according to the described opticglass of any one in claim 1～16, its spectral-transmission favtor is shown as 70% wavelength (λ
70) be below 500nm.
18. according to the described opticglass of any one in claim 1～17, wherein, the value that the transmissivity of the light (d ray) of the following wavelength 587.56nm that reheats the test film after test (A) obtains divided by the transmissivity of the described d ray that reheats the test film before test is more than 0.95
Reheat test (A): test film 15mm * 15mm * 30mm is reheated, from the temperature that is warming up to high 80 ℃ of transition temperature (Tg) than each sample in 150 minutes for room temperature, at the temperature of high 80 ℃ of the second-order transition temperature than described opticglass (Tg), insulation is 30 minutes, then naturally cool to normal temperature, after the relative two sides by test film is ground to thickness 10mm, carry out visual observation.
19., according to the described opticglass of any one in claim 1～18, wherein, the described transmissivity that reheats the front test film of test (A) becomes 70% wavelength X
70with the described λ that reheats the test film after test
70difference be below 20nm,
Reheat test (A): test film 15mm * 15mm * 30mm is reheated, from the temperature that is warming up to high 80 ℃ of transition temperature (Tg) than each sample in 150 minutes for room temperature, at the temperature of high 80 ℃ of the second-order transition temperature than described opticglass (Tg), insulation is 30 minutes, then naturally cool to normal temperature, after the relative two sides by test film is ground to thickness 10mm, carry out visual observation.
20. an attrition process with and/or the preform used of precision press molding, it is to be formed by the described opticglass of any one in claim 1～19.
21. an optical element, it is the described opticglass of any one in claim 1～19 to be carried out to grinding and/or grinding forms.
22. an optical element, it is the described opticglass of any one in claim 1～19 to be carried out to precision press molding form.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011073356A JP2012206891A (en) | 2011-03-29 | 2011-03-29 | Optical glass, perform, and optical device |
| JP2011-073357 | 2011-03-29 | ||
| JP2011073357A JP2012206892A (en) | 2011-03-29 | 2011-03-29 | Optical glass, perform, and optical device |
| JP2011-073356 | 2011-03-29 | ||
| PCT/JP2012/057955 WO2012133420A1 (en) | 2011-03-29 | 2012-03-27 | Optical glass, preform, and optical element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103476722A true CN103476722A (en) | 2013-12-25 |
Family
ID=46931136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800159905A Pending CN103476722A (en) | 2011-03-29 | 2012-03-27 | Optical glass, preform and optical element |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN103476722A (en) |
| TW (1) | TW201245078A (en) |
| WO (1) | WO2012133420A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555784A (en) * | 2017-08-04 | 2018-01-09 | 苏州端景光电仪器有限公司 | A kind of optical glass containing caesium and preparation method and application |
| CN109476529A (en) * | 2016-07-28 | 2019-03-15 | Ａｇｃ株式会社 | Optical Glass and Optical Components |
| CN109956666A (en) * | 2017-12-22 | 2019-07-02 | Hoya株式会社 | Optical glass and optical element |
| CN111170631A (en) * | 2016-09-05 | 2020-05-19 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass |
| CN111892298A (en) * | 2020-09-08 | 2020-11-06 | 成都光明光电股份有限公司 | Optical glass, optical preform and optical element |
| CN111977974A (en) * | 2020-09-08 | 2020-11-24 | 成都光明光电股份有限公司 | Optical glass, optical preform, optical element and optical instrument |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113165954A (en) * | 2018-11-30 | 2021-07-23 | 日本光硝子株式会社 | Optical glass, optical element, optical system, interchangeable lens, and optical device |
| WO2021193176A1 (en) * | 2020-03-24 | 2021-09-30 | 株式会社 オハラ | Chemically strengthened optical glass |
| US11999651B2 (en) | 2020-09-10 | 2024-06-04 | Corning Incorporated | Silicoborate and borosilicate glasses having high refractive index and low density |
| US11976004B2 (en) | 2020-09-10 | 2024-05-07 | Corning Incorporated | Silicoborate and borosilicate glasses having high refractive index and high transmittance to blue light |
| US11802073B2 (en) | 2020-09-10 | 2023-10-31 | Corning Incorporated | Silicoborate and borosilicate glasses with high refractive index and low density |
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| BR8605356A (en) * | 1985-11-29 | 1987-08-04 | Corning Glass Works | GLASS FOR OPTICAL AND / OR OPHTHALMIC APPLICATIONS |
| CN102471130A (en) * | 2009-08-07 | 2012-05-23 | 株式会社小原 | Optical glass |
-
2012
- 2012-03-27 CN CN2012800159905A patent/CN103476722A/en active Pending
- 2012-03-27 WO PCT/JP2012/057955 patent/WO2012133420A1/en active Application Filing
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| US4390638A (en) * | 1980-07-14 | 1983-06-28 | Schott Glaswerke | Acidproof, hydrolysis-resistant optical and ophthalmic glass of low density |
| US4742028A (en) * | 1985-11-29 | 1988-05-03 | Corning Glass Works | Optical and ophthalmic glasses |
| CN101497494A (en) * | 2008-01-31 | 2009-08-05 | 株式会社小原 | Optical glass |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476529A (en) * | 2016-07-28 | 2019-03-15 | Ａｇｃ株式会社 | Optical Glass and Optical Components |
| CN111170631A (en) * | 2016-09-05 | 2020-05-19 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass |
| CN107555784A (en) * | 2017-08-04 | 2018-01-09 | 苏州端景光电仪器有限公司 | A kind of optical glass containing caesium and preparation method and application |
| CN109956666A (en) * | 2017-12-22 | 2019-07-02 | Hoya株式会社 | Optical glass and optical element |
| CN109956666B (en) * | 2017-12-22 | 2023-01-06 | Hoya株式会社 | Optical glass and optical element |
| CN111892298A (en) * | 2020-09-08 | 2020-11-06 | 成都光明光电股份有限公司 | Optical glass, optical preform and optical element |
| CN111977974A (en) * | 2020-09-08 | 2020-11-24 | 成都光明光电股份有限公司 | Optical glass, optical preform, optical element and optical instrument |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201245078A (en) | 2012-11-16 |
| WO2012133420A1 (en) | 2012-10-04 |
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Application publication date: 20131225 |